CN101636270B - Reinforced silicone resin films - Google Patents

Reinforced silicone resin films Download PDF

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Publication number
CN101636270B
CN101636270B CN2008800060503A CN200880006050A CN101636270B CN 101636270 B CN101636270 B CN 101636270B CN 2008800060503 A CN2008800060503 A CN 2008800060503A CN 200880006050 A CN200880006050 A CN 200880006050A CN 101636270 B CN101636270 B CN 101636270B
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silicones
sio
silicon
silicone resin
polymeric layer
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CN101636270A (en
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朱毕忠
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Dow Silicones Corp
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Dow Corning Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • Y10T428/24967Absolute thicknesses specified
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • Y10T428/24967Absolute thicknesses specified
    • Y10T428/24975No layer or component greater than 5 mils thick
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Abstract

Reinforced silicone resin films comprising at least two polymer layers, wherein at least one of the polymer layers comprises a cured product of a at least one silicone resin having an average of at least two silicon-bonded hydrogen atoms, hydroxyl groups, or hydrolysable groups per molecule, and at least one of the polymer layers comprises a carbon nanomaterial.

Description

Strengthen silicone resin film
Relate to the cross reference of application
Do not have
Technical field
The present invention relates to strengthen silicone resin film; Relate more specifically to comprise the enhancing silicone resin film of at least two polymeric layers; Wherein at least one polymeric layer comprises the solidfied material of at least a silicones; Have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in average each molecule of this silicones, at least one polymeric layer comprises carbon nanomaterial.
Background technology
Silicones is of many uses because of its unique combination property such as high thermal stability, high moisture resistance, high-flexibility, high antioxygen property, low capacitivity and the high grade of transparency.For example, silicones is widely used in protection or the dielectric coat in automation, electronization, building, electrical equipment and the aerospace industry.
Although silicone coatings can be used for protection, insulation or connecting circuit substrate, because tearing toughness is low, fragility is high, glass transition temperature is low and thermal coefficient of expansion is high, silicone resin film uses separately and is restricted.Therefore, need to improve the independently silicone resin film of mechanical performance and hot property.
Summary of the invention
Enhancing silicone resin film according to the invention mainly is made up of following:
First polymeric layer; And
The second polymer layer on first polymeric layer; Wherein at least one polymeric layer comprises the solidfied material of at least a silicones; Have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones; And at least one polymeric layer comprises carbon nanomaterial; When if two polymeric layers all comprise the solidfied material of silicones, two polymeric layers all comprise and are selected from (i) carbon nanomaterial, (ii) fabric reinforcement and (iii) comprise (i) and the reinforce of mixture (ii).
Enhancing silicones mould according to the invention also comprises:
First polymeric layer;
The second polymer layer on first polymeric layer; And
At least one additional polymer on the second polymer layer; At least one polymeric layer comprises the solidfied material of at least a silicones, have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones, and at least one polymeric layer comprises carbon nanomaterial.
Enhancing silicones of the present invention has low thermal coefficient of expansion, shows high heat resistanceheat resistant and causes tear resistance.
Enhancing silicones of the present invention can be used for the situation that the requirement film has high thermal stability, pliability, mechanical strength and transparency.For example, silicone resin film can be used for integrated component, solar cell, flexible PCB, touch-screen, fire prevention wallpaper and the high strength window of flexible display.This film also is applicable to the substrate of transparent or opaque electrode.
Description of drawings
Figure 1A strengthens silicone resin film before heat treatment, to overlook microphoto (being top view) in the example 3.
Figure 1B strengthens the cross section microphoto of silicone resin film before heat treatment in the example 3.
Fig. 1 C strengthens silicone resin film after heat treatment, to overlook microphoto in the example 3.
Fig. 2 A and 2B be the silicone resin film that do not strengthen in the comparative example 1 before and after heat treatment separately overlook microphoto.
Fig. 3 strengthens silicone resin film after heat treatment, to overlook microphoto in the example 4.
Fig. 4 strengthens silicone resin film after heat treatment, to overlook microphoto in the example 5.
Only in the accompanying drawings, um representes micron.
The specific embodiment
Use among the application " hydrogen atom, hydroxyl or hydrolysising group account for R in the silicones 2The some mol% numbers of group " be meant R in molal quantity and the resin of the hydrogen atom, hydroxyl or the hydrolysising group that are connected with silicon atom in the silicones 2The ratio of group total mole number multiply by 100.And " hydrogen atom, hydroxyl or hydrolysising group account for R in the silicones 4The some mol% numbers of group " be meant R in molal quantity and the resin of the hydroxyl that is connected with silicon atom in the silicones or hydrolysising group 4The ratio of group total mole number multiply by 100.
Of the present invention first strengthens silicone resin film mainly is made up of following:
First polymeric layer; And
The second polymer layer on first polymeric layer; Wherein at least one polymeric layer comprises the solidfied material of at least a silicones; Have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones; And at least one polymeric layer comprises carbon nanomaterial; When if two polymeric layers all comprise the solidfied material of silicones, two polymeric layers all comprise and are selected from (i) carbon nanomaterial, (ii) fabric reinforcement and (iii) comprise (i) and the reinforce of mixture (ii).
First strengthen silicone resin film the common thickness of first polymeric layer be 0.01 μ m to 1000 μ m, or 5 μ m to 500 μ m, again or 10 μ m to 100 μ m.
First polymeric layer of the first enhancing silicone resin film can comprise thermoplastic polymer or thermosetting polymer.Thermoplastic polymer or thermosetting polymer can be homopolymers or copolymer.In addition, thermoplasticity or thermosetting polymer can be silicon polymer or organic polymer.As here and hereinafter used, " thermoplastic polymer " is meant when heating and is converted into fluid (can flow) state, become the polymer of rigidity (not flowing) state when catching a cold.In addition, " thermosetting polymer " is meant the cure polymer (crosslinked) that does not become fluid state when being heated.
The example of thermoplastic polymer includes, but is not limited to: the thermoplasticity silicon polymer, as gather (diphenyl siloxane-copolymerization-benzyl siloxanes) and thermoplastic organic polymer such as polyolefin, polysulfones, polyacrylate and PEI.
The example of thermosetting polymer includes, but is not limited to the thermosetting silicon polymer, like solidification of silicon elastomer, silica gel and solidification of silicon resin; And thermosetting organic polymer such as epoxy resin, curing amino resin, solidify bimaleimide resin, curing polyester and curing acrylic resin.
Except thermoplasticity or thermosetting polymer, first polymeric layer of the first enhancing silicone resin film can also comprise the reinforce that is selected from carbon nanomaterial, fabric reinforcement and composition thereof, as following said.
The second polymer layer of the first enhancing silicone resin film is of first polymeric layer.First and second polymeric layers that strengthen silicone resin film there are differences aspect some physics, the chemical property at least, like the concentration of thickness, component of polymer, crosslink density and carbon nanomaterial or other reinforces etc.
At least one polymeric layer of the first enhancing silicone resin film comprises the solidfied material of at least a silicones, has at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones." solidfied material of at least one silicones " as used herein is meant the cross-linking products of at least one silicones, and this product comprises tridimensional network.Silicones, prepare the method for this resin, and the method for preparing the silicones solidfied material, is described to some extent in following preparation first in strengthening the method for silicone resin film.
At least one polymeric layer of the first enhancing silicone resin film comprises carbon nanomaterial.Carbon nanomaterial can be the material with carbon element of any physical size (for example, particle diameter, fibre diameter, layer thickness) less than about 200nm.The example of carbon nanomaterial includes, but is not limited to three-dimensional dimension less than about 200nm carbon nano-particle, for example the point of quantum stage, empty spheroid and Fu Leqiu; Two-dimension sizes is less than the fibrous carbon nano material of about 200nm, like nanotube (for example single-walled nanotube and many walls nanotube) and nanofiber (for example, axial orientation, tabular and herringbone or herringbone); And have the layered carbon nano material of one dimension size less than about 200nm, like carbon nanometer layer (for example, flake graphite and graphite flake).Carbon nanomaterial can be a conduction or semiconductive.Carbon nanomaterial can also be the carbon nanomaterial of oxidation, and it can handle aforesaid carbon nanomaterial obtaining through using oxidizing acid or at high temperature mixing with acid.For example, carbon nanomaterial can be able to oxidation in 1 hour to 3 hours through material and the nitric acid that concentrates or sulfuric acid (1: 3v/v, 25mL/g carbon) heating under 40 ℃ to 150 ℃.
Carbon nanomaterial can be that single carbon nanomaterial also can be the mixture that comprises at least two kinds of different carbon nanomaterials, explains separately shown in the hereinafter content.
First and/or the second polymer layer in the concentration of carbon nanomaterial be generally 0.0001% to 99% (w/w) of polymeric layer gross weight; Or 0.001% to 50% (w/w); Or 0.01% to 25% (w/w), or 0.1% to 10% (w/w), or 1% to 5% (w/w).
The method for preparing carbon nanomaterial is known by the people in the art.For example carbon nano-particle (for example richness is reined in ball) and fibrous carbon nano material (for example, nanotube and nanofiber) can make through a kind of method below at least: arc discharge, cut and chemical catalysis vapour deposition etc.In arc discharge method, different according to atmosphere, the arc discharge that between two graphite electrodes, produces can generate single-walled nanotube, many walls nanotube and Fu Leqiu.In laser cutting method, the graphite target that deposits metallic catalyst generates single wall and many walls nanotube through laser irradiation in tube furnace.In the chemical catalysis vapour deposition process, carbonaceous gas or admixture of gas are introduced and are contained metallic catalyst, temperature in the tube furnace of 500 ℃ to 1000 ℃ (under the different pressures), generate CNT and nanofiber.Carbon nanosheet can obtain through graphite intercalation and layering.
When first strengthen silicone resin film two polymeric layers when all comprising the solidfied material of silicones, then two polymeric layers all comprise and are selected from (i) carbon nanomaterial, (ii) fabric reinforcement and (iii) comprise (i) and the reinforce of mixture (ii).Carbon nanomaterial is described as above.Polymeric layer all can comprise identical or different being selected from (i), (ii) and reinforce (iii).
As long as reinforce has high-modulus and high-tensile, then fabric reinforcement can be any reinforce that comprises fiber.Fabric reinforcement has the Young's modulus of 3GPa at least usually in the time of 25 ℃.For example, when the common Young's modulus of reinforce is 25 ℃, 3GPa to 1000GPa, or 3GPa to 200GPa, or 10GPa to 100GPa.In addition, reinforce has the tensile strength of 50MPa at least usually in the time of 25 ℃.For example, when the common tensile strength of reinforce is 25 ℃, 50MPa to 10000MPa, or 50MPa to 1000MPa, or 50MPa to 500MPa.
Fabric reinforcement can be a fabric, for example: cloth; Non-woven fibre, for example: felt or yarn; Or loose (independent body) fiber.Fiber in the reinforce is generally cylindrical, and diameter has 1 μ m to 100 μ m, or 1 μ m to 20 μ m, or 1 μ m to 10 μ m.Loose fiber both can be continuous, and promptly fiber does not pass the enhancing silicone resin film with roughly not rupturing, can break off yet.
Fabric reinforcement is heat-treated usually before use, to remove organic impurities.For example, fabric reinforcement is the suitable time of heating in air usually, as 2 hours, is heated to for example 575 ℃.
The example of fabric reinforcement includes, but is not limited to: the reinforce that contains glass fibre; Quartz fibre; Graphite fibre; Nylon fiber; Polyester fiber; Aramid fibre such as Kevlar
Figure G2008800060503D00041
and Nomex
Figure G2008800060503D00042
; Polyethylene fibre; Polypropylene fibre and diamond dust fiber.
First and/or the concentration of the fabric reinforcement of the second polymer layer be generally 0.1% to 95% (w/w) of polymeric layer gross weight, or 5% to 75% (w/w), or 10% to 40% (w/w).
When one or two polymeric layer of the first enhancing silicone resin film comprises the mixture of carbon nanomaterial and fabric reinforcement; The concentration of mixture is generally 0.1% to 96% (w/w) of polymeric layer gross weight; Or 5% to 75% (w/w), or 10% to 40% (w/w).
First polymeric layer and the second polymer layer can strengthen the method preparation of silicone resin film through the preparation first that is described below.
First strengthens silicone resin film can prepare through the method that comprises following content:
On barrier film, form first polymeric layer; And
On first polymeric layer, form the second polymer layer; Wherein at least one polymeric layer comprises the solidfied material of at least a silicones; Have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones; And at least one polymeric layer comprises carbon nanomaterial; When if two polymeric layers all comprise the solidfied material of silicones, two polymeric layers all comprise and are selected from (i) carbon nanomaterial, (ii) fabric reinforcement and (iii) comprise (i) and the reinforce of the mixture of (i i).
Strengthen in the first step of silicone resin film in preparation first, as stated, first polymeric layer forms on barrier film.
Barrier film can be any rigidity or flexible material that can make first polymeric layer not have damage from its surface removal and to the surface.Example includes, but is not limited to: silicon, quartz, vitreosil, aluminium oxide, pottery, glass, tinsel, polyolefin such as polyethylene, polypropylene, polystyrene and PET; Fluorocarbon polymer such as polytetrafluoroethylene (PTFE) and vinyl polymerization fluoride; Polyamide such as nylon; Polyimides; Polyester is as gathering (methacrylate); Epoxy resin; Polyethers; Merlon; Polysulfones; And polyester sulfone.Barrier film can also be a surface process releasing agent, like silicon mold release agent, and the above-mentioned material of processing.
First polymeric layer can be different according to the composition of polymeric layer, make through several different methods.For example, when first polymeric layer comprised thermoplastic polymer, this layer can have the barrier film of liquid thermoplastic polymer synthetic through (i) coating, and (ii) changes into the polymer on the barrier film of coating solid-state.
In step (i), form in the method for first polymeric layer, be coated with the synthetic that comprises the liquid thermoplastic polymer on the above-mentioned barrier film.
The synthetic that includes thermoplastic polymer can be any synthetic that includes liquid state (being liquid) thermoplastic polymer.As " the liquid thermoplastic polymer " mentioned here is meant the polymer that is in molten state or is dissolved in the polymer in the organic solvent.For example, synthetic can comprise and is higher than the thermoplastic polymer that melting point polymer (Tm) or glass transition temperature (Tg) are in molten state, can also comprise thermoplastic polymer and organic solvent.
The thermoplastic polymer of synthetic above-mentioned can be used for making the enhancing silicone resin film.Thermoplastic polymer can be that independent a kind of thermoplastic polymer also can be the mixture (being fusion) that comprises two or more different thermoplastic polymers.For example, thermoplastic polymer can be a polyolefin blend.
Organic solvent can be any proton solvent, aprotic solvent or not react with thermoplastic polymer and be prone to and the thin proton-organic solvent of the dipole of mixed with polymers.Representative examples of organic includes, but is not limited to: saturated aliphatic hydrocarbon, like pentane, hexane, normal heptane, isooctane and dodecane; Clicyclic hydrocarbon such as cycloheptane and cyclohexane; Aromatic hydrocarbon is like benzene,toluene,xylene and trimethylbenzene; Cyclic ethers such as oxolane (THF) and dioxane; Ketone such as methyl butene ketone (MIBK); Halogenated alkane is like trichloro-ethylene; Halogenated aromatic such as bromobenzene and chlorobenzene; And alcohol is like methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, one-butanols, 2-butanols, 2-methyl-1-butene alcohol, 1,1-dimethyl-1-ethanol, amylalcohol, hexanol, cyclohexanol, enanthol and octanol.
Organic solvent can be that independent a kind of organic solvent above-mentioned also can be the mixture of two or more organic solvent.
The synthetic that includes thermoplastic polymer can further include carbon nanomaterial above-mentioned.
Can be coated with the liquid synthetic that comprises thermoplastic polymer through traditional coating process on the barrier film, coating process has method of spin coating, embathes method, spraying process, brushing method, extrusion or silk screen print method.The amount of synthetic enough prepares first polymeric layer that thickness is 0.01 μ m to 1000 μ m.
Step (ii) in, the thermoplastic polymer of barrier film is converted into solid-state.When the synthetic that is used for being coated with barrier film included the thermoplastic polymer of molten state, polymer was cooled to solid-liquid transformation temperature (Tg or Tm), and below room temperature, thermoplastic polymer can be converted into solid-state.When the synthetic that is used for being coated with barrier film comprised thermoplastic polymer and organic solvent, thermoplastic polymer can change into solid-state through removing the means of at least a portion solvent.Organic solvent can be able to remove through evaporating solvent towards periphery or the method that is warming up to proper temperature (as being lower than polymer solid-liquid transformation temperature) heating coating.
Preparation comprises the method for first polymeric layer of thermoplastic polymer, can also further comprise in step (i) with (ii): what in first step, obtain applies second layer barrier film on the barrier film of coating, form lamination, and this lamination is compressed.This lamination can be removed superfluous components and/or be retained in air wherein through compression, to reduce the thickness of coating.Can adopt legacy equipment to lamination, like stainless steel rider, hydraulic pressure, rubber rollers or lamination combination roller.Lamination is through compressing in the temperature range between the pressure of 1000Pa to 10MPa, room temperature (about 23 ± 2 ℃) are to 200 ℃.
Preparation includes the method for first polymeric layer of thermoplastic polymer, if each coating is all used identical composition, can further include the step (i) that repeats with (ii), with the thickness of increase polymeric layer.
When first polymeric layer comprised thermosetting polymer (promptly crosslinked), this layer can be coated with barrier film with the cure component that includes thermosetting polymer through (i), (ii) the thermosetting polymer on the barrier film of coating is cured.
In the back to back step (i), above-mentioned barrier film is coated with cure component before the method for preparation first polymeric layer, and this composition comprises thermosetting polymer.
The curable synthetic that includes thermosetting polymer can be any curable synthetic that includes thermosetting polymer.As here with " thermosetting polymer " hereinafter mentioned be meant possess through overcuring (promptly crosslinked) just permanent deformation become the polymer of rigidity (can not flow) performance.Curable synthetic generally includes thermosetting polymer and adding ingredient, like organic solvent, crosslinking agent and/or catalyst.
The example that includes the curable synthetic of thermosetting polymer includes, but is not limited to: curable silicon synthetic, like hydrosilylation-solidification of silicon synthetic, concentrated-solidification of silicon synthetic and peroxidating-solidification of silicon synthetic; Solidify polyolefin synthetic such as polyethylene and polypropylene synthetic; Solidify polyamide synthesized substance; The cured epoxy resin synthetic; The curing amino resin composition; The curing urethane synthetic; The cure polyimide synthetic; Curing polyester synthetic and curing acrylic resin composition.
The curable synthetic that comprises thermosetting polymer can also be to include concentrating-the solidification of silicon synthetic of silicones, and comprises at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones.
Concentrate-the solidification of silicon synthetic can be any silicones that includes, and comprise concentrating-the solidification of silicon synthetic of at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this resin.Usually, concentrated-solidification of silicon synthetic comprises the silicones of signature, and optionally comprises crosslinking agent and/or the catalyst concentration with the hydrolysising group that is connected with silicon atom.
Usually, concentrate-the solidification of silicon synthetic is to contain the copolymer that T unit, T and Q siloxane unit or T and/or Q siloxane unit combine with M and/or D siloxane unit.In addition, silicones can be the silicones of modified rubber, and that hereinafter is described is second embodiment of concentrated-solidification of silicon synthetic.
According to first embodiment, if comprise at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in average each molecule of silicones, concentrated-solidification of silicon synthetic comprises that molecular formula is (R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) z(I) silicones, wherein R 1Be C 1To C 10Alkyl or C 1To C 10The substituted alkyl of halogen, R 2Be R 1,-H ,-OH or hydrolysising group, the w value is 0 to 0.95, and the x value is 0 to 0.95, and the y value is 0 to 1, and the z value is 0 to 0.95, and w+x+y+z=1, y+z are 0.05 to 1, and w+x is 0 to 0.95.
By R 1The alkyl and the halo alkyl of expression have 1 to 10 carbon atom usually, or 1 to 6 carbon atom, or 1 to 4 carbon atom.Comprise the structure that at least 3 carbon atom acrylic acid hydrocarbon and halo alkyl can contain grafting or not grafting.By R 1The example of the alkyl of expression includes, but is not limited to: alkyl such as methyl, ethyl, propyl group, 1 Methylethyl, butyl, 1 methyl-propyl, 2 methyl-propyls, 1; 1 dimethyl ethyl, amyl group, 1 methyl butyl, 1 ethyl propyl, 2 methyl butyls, 3 methyl butyls, 1; 2 dimethyl propyls, 2,2 dimethyl propyls, hexyl, heptyl, octyl group, nonyl and decyl; Cyclic hydrocarbon radical such as cyclopenta, ring octyl group and methyl ring octyl group; Aryl such as phenyl and naphthyl; Alkaryl such as tolyl and xylyl; Aralkyl such as benzyl and phenethyl; Alkylene such as vinyl, pi-allyl and acrylic; Arylalkenyl such as styryl and cinnamyl group; With alkynyl such as acetenyl and propinyl.R 1The example of the haloalkyl of representative includes, but is not limited to: 3,3, and 3-trifluoropropyl alkyl, 3-chloro-propane base, chlorophenyl, dichloro-phenyl, 2,2,2-three fluoro ethyls, 2; 2,3, the 3-tetrafluoro is for propyl group and 2,2,3; 3,4,4,5, the hot fluoro pentyl of 5-.
As " hydrolysising group " mentioned here is meant having catalyst to exist or do not having under the catalyst existence condition; In the temperature range of room temperature (about 23 ± 2 ℃) between 100 ℃; In the time of some minutes (as 30 minutes), group that is connected with silicon and water reaction form silanol (Si-OH) group.R 2The example of the hydrolysising group of expression includes, but is not limited to :-Cl ,-Br ,-OR 3,-OCH 2CH 2OR 3, CH 2C (=O) O-, Et (Me) C=N-O-, CH 3C (=O) N (CH 3)-and-ONH2, wherein R 3Be C 1To C 8Alkyl or C 1To C 8The halo alkyl.
R 3The alkyl and the halo alkyl of expression have 1 to 8 carbon atom usually, or 3 to 6 carbon atoms.Include at least 3 fat of carbon atom family alkyl and halo alkyl and can have the structure of grafting or not grafting.R 3The example of the alkyl of expression includes, but is not limited to: the alkyl of not grafting and grafting such as methyl, ethyl, propyl group, 1 Methylethyl, butyl, 1 methyl-propyl, 2 methyl-propyls, 1; 1 dimethyl ethyl, amyl group, 1 methyl butyl, 1 ethyl propyl, 2 methyl butyls, 3 methyl butyls, 1; 2 dimethyl propyls, 2,2 dimethyl propyls, hexyl, heptyl and octyl group; Cyclic hydrocarbon radical such as cyclopenta, ring octyl group and methyl ring octyl group; Aryl such as phenyl and naphthyl; Alkylene such as vinyl, pi-allyl and acrylic; Aralkyl such as phenethyl; Alkynyl such as acetenyl and propinyl R 3The example of the halo alkyl of representative includes, but is not limited to: 3,3, and 3-trifluoropropyl alkyl, 3-chloro-propane base, chlorophenyl, dichloro-phenyl.
In the formula (I) of silicones, subscript w, x, y and z are molfraction.Subscript w value is generally 0 to 0.95, or 0.02 to 0.75, or 0.05 to 0.3; Subscript x value is generally 0 to 0.95, or 0 to 0.7, or 0 to 0.25; Subscript y value is generally 0 to 1, or 0.25 to 0.8, or 0.5 to 0.8; Subscript z value is generally 0 to 0.95, or 0 to 0.7 or 0 to 0.15.And the y+z sum is generally 0.05 to 1, or 0.5 to 0.95, or 0.65 to 0.9.In addition, the w+x sum is generally 0 to 0.95, or 0.05 to 0.5, or 0.1 to 0.35.
Usually, 1mol% at least in the silicones, or 10mol% at least, or the R of 50mol% at least 2Be hydrogen atom, hydroxyl or hydrolysising group.
The common number-average molecular weight of silicones (Mn) is 500 to 50000, or 500 to 10000, or 1000 to 3000, wherein molecular weight is to utilize low angle laser light scattering appearance or refractive power detector, and silicones (MQ) standard adopts gel permeation chromatography to obtain.
Under 25 ℃, the viscosity of silicones is generally 0.01Pa.s to 100000Pa.s, or 0.1Pa.s to 10000Pa.s, or 1Pa.s to 100Pa.s.
Silicones comprises R 2SiO 3/2Unit (being the T unit), R 2SiO 3/2Unit (being the T unit) and SiO 4/2Unit (being the Q unit) or R 2SiO 3/2Unit (being the T unit) and/or SiO 4/2Unit (being the Q unit) and R 1R 2 2SiO 1/2Unit (being the M unit) and/or R 2 2SiO 2/2Unit (being the D unit), wherein R 1And R 2As stated.For example, silicones can be T resin, TQ resin, DT resin, MT resin, MDT resin, MQ resin, DQ resin, MDQ resin, MTQ resin, DTQ resin or MDTQ resin.
The example of silicones includes, but is not limited to have the resin of following molecular formula:
(MeSiO 3/2)n,(PhSiO 3/2)n,(Me 3SiO 1/2) 0.8(SiO 4/2) 0.2,(MeSiO 3/2) 0.67(PhSiO 3/2) 0.33
(MeSiO 3/2) 0.45(PhSiO 3/2) 0.40(Ph 2SiO 2/2) 0.1(PhMeSiO 2/2) 0.05
(PhSiO 3/2) 0.4(MeSiO 3/2) 0.45(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.05And
(PhSiO 3/2) 0.4(MeSiO 3/2) 0.1(PhMeSiO 2/2) 0.5
Wherein Me is a methyl, and Ph is a phenyl, and the outer index number of bracket is represented molfraction, and the value of subscript n makes the number-average molecular weight of silicones reach 500 to 50000.In addition, in the molecular formula in front, the order of unit does not fix.
Concentrated-first embodiment of solidification of silicon synthetic can comprise the mixture of above-mentioned independent a kind of silicones or two or more Different Silicon resin.
The method that preparation includes the silicones of the hydrogen atom, hydroxyl or the hydrolysising group that are connected with silicon is the known method of this area; These resins also can have been bought mostly.Silicones normally organic solvent (like toluene), in suitably mix that the silicon precursor cohydrolysis obtains.For example silicones can be R through cohydrolysis molecular formula in toluene 1R 2 2The silane of SiX and molecular formula are R 2SiX 3Silane obtain R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 2Be R 1, or hydrolysising group, X is a hydrolysising group, prerequisite is R 2Be hydrolysising group, X compares R in hydrolysis 2Reactivity is higher.Separated salt aqueous acid and silicon hydrolysate, water flushing water hydrolysis products is removed residual acid, and heating makes resin " plastotype " (promptly concentrating) obtain needed viscosity under suitable catalyst concentration existence condition.If desired, resin can also use catalyst concentration in organic solvent, further to handle, and reduces the content of the hydroxyl that is connected with silicon atom.
Concentrate-first embodiment of solidification of silicon synthetic can comprise adding ingredient, prerequisite be this composition can not hinder silicones solidify to form be described below have low thermal coefficient of expansion, the solidification of silicon resin of high-tensile and HMW.The example of adding ingredient includes, but is not limited to: tackifier, coloring agent, pigment, antioxidant, heat stabilizer, ultra-violet stabilizer, fireproof agent, levelling agent, organic solvent, crosslinking agent and catalyst concentration.
For example the silicones synthetic can also comprise crosslinking agent and/or catalyst concentration.Crosslinking agent can have R 3 qSiX 4-qMolecular formula, R wherein 3Be C 1To C 8Alkyl or C 1To C 8The halo alkyl, X is a hydrolysising group, q is 0 or 1.By R 3The alkyl or the halo alkyl of representative, the hydrolysising group of X representative as stated.
The example of crosslinking agent includes, but is not limited to: alkoxy silane as
MeSi(OCH 3) 3,CH 3Si(OCH 2CH 3) 3,CH 3Si(OCH 2CH 2CH 3) 3,CH 3Si[O(CH 2) 3CH 3] 3
CH 3CH 2Si(OCH 2CH 3) 3,C 6H 5Si(OCH 3) 3,C 6H 5CH 2Si(OCH 3) 3,C 6H 5Si(OCH 2CH 3) 3
CH 2=CHSi(OCH 3) 3,CH 2=CHCH 2Si(OCH 3) 3,CF 3CH 2CH 2Si(OCH 3) 3
CH 3Si(OCH 2CH 2OCH 3) 3,CF 3CH 2CH 2Si(OCH 2CH 2OCH 3) 3
CH 2=CHSi(OCH 2CH 2OCH 3) 3,CH 2=CHCH 2Si(OCH 2CH 2OCH 3) 3
C 6H 5Si (OCH 2CH 2OCH 3) 3, Si (OCH 3) 4, Si (OC 2H 5) 4And Si (OC 3H 7) 4
Organic acetate silane such as CH 3Si (OCOCH 3) 3, CH 3CH 2Si (OCOCH 3) 3And CH 2=CHSi (OCOCH 3) 3Organic imino group siloxanes such as CH 3Si [O-N=C (CH 3) CH 2CH 3] 3, Si [O-N=C (CH 3) CH 2CH 3] 4And CH 2=CHSi [O-N=C (CH 3) CH 2CH 3] 3Organic acetamide silane such as CH 3Si [NHC (=O) CH 3] 3And C 6H 5Si [NHC (=O) CH 3] 3Amino silicone such as CH 3Si [NH (s-C 4H 9)] 3And CH 3Si (NHC 6H 11) 3And organic amino radical siloxane.
Crosslinking agent can be independent a kind of siloxanes above-mentioned or two or more different silane.In addition, preparing the method with three or four functional group's siloxanes is method as known in the art; These silane can buy mostly.
Under its existence condition, crosslinking agent enough makes silicones solidify (crosslinked) in the silicones synthetic.Definitely measuring certainly in the state of cure of being wanted of crosslinking agent, it increases along with the increase of the ratio of the molal quantity of the hydrogen atom, hydroxyl or the hydrolysising group that are connected with silicon atom in the molal quantity of the hydrolysising group that links to each other with silicon atom in the crosslinking agent and the silicones.Usually, the concentration of crosslinking agent enough provides 0.2 to 4 mole of hydrolysising group that links to each other with silicon atom for every mole of hydrogen atom that links to each other with silicon atom, hydroxyl or hydrolysising group in the silicones.Just can obtain the preferred amounts of required crosslinking agent through routine experimentation.
First embodiment of the silicon synthetic that concentrates as stated ,-solidify can further include at least a catalyst concentration.Catalyst concentration can be any catalyst concentration that hydroxyl (silanol) concentration that links to each other with silicon forms the Si-O-Si type of attachment that is commonly used to improve.The example of catalyst concentration includes, but is not limited to: the complex compound of amine, lead, tin, zinc and iron and carboxylic acid.Specifically, catalyst concentration can be selected from the compound of tin (II) and tin (IV), like tin laurate, two tin octoates and tetrabutyltin and titanium compound, like four butanols titaniums.
During use, the concentration of catalyst concentration is generally 0.1% to 10% (w/w) of silicones gross weight, or 0.5% to 5% (w/w), or 1% to 3% (w/w).
According to second embodiment, concentrated-solidification of silicon resin composition comprises the silicones of (A) modified rubber, and it is to be (R by being selected from (i) molecular formula 1R 4 2SiO 1/2) w(R 4 2SiO 2/2) x(R 4SiO 3/2) y(SiO 4/2) z(II) silicones and (ii), the hydrolysis precursor of (i), and molecular formula is R 5 3SiO (R 1R 5SiO) mSiR 5 3The reaction under the condition that has water, catalyst concentration and organic solvent to exist of the organic siliconresin compound of silicone rubber (III) generates the product of solubility, thereby makes, wherein R 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 4Be R 1,-OH or hydrolysising group, R 5Be R 1Or hydrolyzable group, m is 2 to 1000, w is 0 to 0.95; X is 0 to 0.95, and y is 0 to 1, and z is 0 to 0.95; W+x+y+z=1, y+z are 0.05 to 1, and w+x is 0 to 0.95; Prerequisite is in each silicones (II) molecule at least two hydrolysising groups that link to each other with silicon atom to be arranged on average, and in the silicone rubber (III), the hydroxyl that links to each other with silicon atom in the hydrolysising group that links to each other with silicon atom and the silicones (II) or the mol ratio of hydrolysising group are 0.01 to 1.5; Also comprise (B) catalyst concentration.
Composition (A) is the silicones of modified rubber, and it is to be (R by being selected from (i) at least a molecular formula 1R 4 2SiO 1/2) w(R 4 2SiO 2/2) x(R 4SiO 3/2) y(SiO 4/2) z(II) silicones and (ii): hydrolysis precursor (i) and at least a molecular formula are R 5 3SiO (R 1R 5SiO) mSiR 5 3(III) silicone rubber having at organo-silicon compound that reaction generates the product of solubility under the condition that water, catalyst concentration and organic solvent exist, thereby makes, wherein R 1W, x, y, z, y+z, and w+x is identical with above-mentioned silicones with molecular formula (I), by R 4, R 5The hydrolysising group such as the above-mentioned R of representative 2M is 2 to 1000; Precursor is in each silicones (II) molecule at least two hydrolysising groups that link to each other with silicon atom to be arranged on average; On average have two hydrolysising groups that link to each other with silicon atom at least in each molecule of silicon rubber (III), in the silicone rubber (III), the hydroxyl that links to each other with silicon atom in the hydrolysising group that links to each other with silicon atom and the silicones (II) or the mol ratio of hydrolysising group are 0.01 to 1.5.As " the soluble reaction product " mentioned here is meant that the product of prepared composition (A) can be dissolved in the organic solvent, can not form sediment or suspension.
Usually, R in the silicones (i) 410mol% at least, or 50mol% at least, or 80mol% is hydroxyl or hydrolysising group at least.
The common number-average molecular weight (Mn) of silicones (i) is 500 to 50000, or 500 to 10000, or 1000 to 3000, wherein molecular weight is to utilize low angle laser light scattering appearance or refractive power detector, and silicones (MQ) standard adopts gel permeation chromatography to obtain.
Under 25 ℃, the viscosity of silicones is generally 0.01Pa.s to 100000Pa.s, or 0.1 to 10000Pa.s, or 1 to 100Pa.s.
Silicones comprises R 4SiO 3/2Unit (being the T unit), R 4SiO 3/2Unit (being the T unit) and SiO 4/2Unit (being the Q unit) or R 4SiO 3/2Unit (being the T unit) and/or SiO 4/2Unit (being the Q unit) and R 1R 4 2SiO 1/2Unit (being the M unit) and/or R 4 2SiO 2/2Unit (being the D unit), wherein R 1And R 4As stated.For example, silicones can be T resin, TQ resin, DT resin, MT resin, MDT resin, MQ resin, DQ resin, MDQ resin, MTQ resin, DTQ resin or MDTQ resin.
The example of silicones includes, but is not limited to have the resin of following molecular formula:
(MeSiO 3/2) n, (PhSiO 3/2) n, (PhSiO 3/2) 0.4(MeSiO 3/2) 0.45(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.05, and (PhSiO 3/2) 0.3(SiO 4/2) 0.1(Me 2SiO 2/2) 0.2(Ph 2SiO 2/2) 0.4, wherein Me is a phenyl for methyl Ph, and the outer index number of bracket is represented molfraction, and the value of subscript n makes the number-average molecular weight of silicones reach 500 to 50000.In addition, in the molecular formula in front, the order of unit does not fix.
Silicones (i) can be the mixture that above-mentioned independent a kind of silicones or two or more molecular formula are the Different Silicon resin of (II).
The manufacturing approach that can be used as the silicones of silicones (i) belongs to content as known in the art; These resin great majority can have been bought.For example silicones normally respective mixtures through cohydrolysis silicones precursor in the organic solvents such as toluene used when the silicones that preparation as stated has molecular formula (I) obtain.
The organic siliconresin compound can also be the hydrolysable precursors that (ii) has the silicones of molecular formula (II).As " hydrolysable precursors " mentioned here be meant to have hydrolyzable groups, is suitable for having as preparation the silane of beginning material (precursor) of the silicones of molecular formula (II).Hydrolysable precursors can be represented R with following molecular formula 1R 4SiX, R 4 2SiX 2, R 4SiX 3And SiX 4R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 4Be R 1Or hydrolysising group, X is hydrolyzable group.Hydrolysable precursors includes, but is not limited to: the silane with following molecular formula:
Me 2ViSiCl, Me 3SiCl, MeSi (OEt) 3, PhSiCl 3, MeSiCl 3, Me 2SiCl 2, PhMeSiCl 2, SiCl 4, Ph 2SiCl 2, PhSi (OMe) 3, MeSi (OMe) 3, PhMeSi (OMe) 2, and Si (OEt) 4, wherein Me is a methyl, Ph is a phenyl.
The method that preparation has the silane of hydrolyzable groups is the known technology in this area; These compounds can have been bought mostly.
In the molecular formula (III) of silicone rubber, R 1And R 5With above-mentioned disclosed content, the common value of subscript m is 2 to 1000, or 4 to 500, or 8 to 400.
Example with silicone rubber of molecular formula (III) includes, but is not limited to: the silicone rubber with following molecular formula: (EtO) 3SiO (Me 2SiO) 55Si (OEt) 3(EtO) 3SiO (Me 2SiO) 16Si (OEt) 3, (EtO) 3SiO (Me 2SiO) 386Si (OEt) 3, and (EtO) 2MeSiO (PhMeSiO) 10SiMe (OEt) 2, wherein Me is a methyl, the Et ethyl.
Silicone rubber with molecular formula (III) can be independent a kind of silicone rubber or two or more has the mixture of the silicone rubber of molecular formula (III).For example silicone rubber can comprise that dp value (extent of polymerization) is about 15 first silicone rubber and dp value and is about 350 second silicone rubber, and wherein dp representes with m in molecular formula II.
The preparation method who comprises by the silicone rubber of the hydrolyzable groups that links to each other with silicon atom is the method for knowing in this area, and these compound great majority can have been bought.
Catalyst concentration used during the silicones of the modified rubber of prepared composition (A) is said with first embodiment of above-mentioned concentrating-solidification of silicon resin composition.Specifically, titanium compound is suitable to catalyst concentration prepared composition (A).
Organic solvent is a kind of for adopting at least.Organic solvent can be to dredge proton type arbitrarily or dipole is dredged the proton type organic solvent, and it does not react under the condition of following prepared composition (A) with the silicones of organic siliconresin compound, silicone rubber or modified rubber, and is prone to be mixed in aforesaid composition.
Representative examples of organic includes, but is not limited to: aliphatic saturated hydrocarbon, like pentane, hexane, normal heptane, isooctane and dodecane; Clicyclic hydrocarbon such as cycloheptane and cyclohexane; Aromatic hydrocarbon is like benzene,toluene,xylene and trimethylbenzene; Cyclic ethers such as oxolane (THF) and dioxane; Ketone such as methyl butene ketone (MIBK); Halogenated alkane is like trichloro-ethylene; Halogenated aromatic such as bromobenzene and chlorobenzene.Organic solvent can the time above-mentioned independent a kind of organic solvent or two kinds and two or more organic solvents mixture.
Organo-silicon compound, silicone rubber, catalyst concentration and organic solvent can synthesize in random order.Usually organo-silicon compound, silicone rubber and organic solvent synthesize prior to catalyst concentration.
In the silicone rubber, the hydrolysising group that links to each other with silicon atom and molecular formula are 0.01 to 1.5 for the hydroxyl that links to each other with silicon atom in the silicones of (II) or the mol ratio of hydrolysising group, or 0.05 to 0.8, or 0.2 to 0.5.
The concentration of water depends on the R in the organo-silicon compound in the reactant mixture 4The hydrolyzable groups that links to each other with silicon in group and the silicone rubber.When organo-silicon compound comprised hydrolysising group, the concentration of water enough influenced the hydrolytic process of hydrolysising group in organo-silicon compound and the silicone rubber.For instance, the concentration of the corresponding water of every mole hydrolysising group is generally 0.01 to 3 mole in organo-silicon compound and the silicone rubber, or 0.05 to 1 mole.When organo-silicon compound do not contain hydrolysising group, in reactant mixture, only need the water of micro-concentrations, for example 100ppm.Usually in reactant and/or solvent, there is low amounts of water.
The concentration response of enough catalysis organo-silicon compound of the concentration of catalyst concentration and silicone rubber.Usually, the concentration of catalyst concentration is 0.01% to 2% (w/w) of organo-silicon compound gross weight, or 0.01% to 1% (w/w), or 0.05% to 0.2% (w/w).
The concentration of organic solvent is generally 10% to 95% (w/w) of reactant mixture gross weight, or 20% to 85% (w/w), or 50% to 80% (w/w).
Reaction temperature is generally room temperature (about 23 ± 2 ℃) between 180 ℃, or between the room temperature to 100 ℃.
Reaction time depends on Several Factors, includes the structure and the temperature of organic silicon compound and silicone rubber.Usually give each composition certain time length, concentration response fully carries out in addition.This means through 29The nuclear magnetic resonance POP method of Si detects, and allows the composition reaction by to 95mol%, or 98mol%, or till the hydrolysising group that links to each other with silicon atom in the former silicone rubber of 99mol% consumes in concentration response.Between room temperature (about 23 ± 2 ℃) was to 100 ℃, the reaction time was generally 1 to 30 hour.Preferred reaction duration can be through the common experimental means decision described in the following example part.
Concentrating-second embodiment of solidification of silicon resin composition in, the silicones of modified rubber can need not to separate or purify, also can more can traditional distillating method separation resin from most of solvent.For example, through reacting by heating mixture under the condition of decompression.
In second embodiment of concentrated-solidification of silicon resin composition, composition (B) is at least a catalyst concentration.Wherein catalyst is the catalyst described in first embodiment of silicones synthetic.Specifically, zinc compound and amine are suitable to changing the composition (B) in the silicon synthetic.
The concentration of composition (B) is generally 0.1% to 10% (w/w) of composition (A) gross weight, or 0.5% to 5% (w/w), or 1% to 3% (w/w).
Second embodiment of concentrated-solidification of silicon resin composition can comprise additive, and prerequisite is that the material that adds can not stop the curing of silicones, thereby forms the solidification of silicon resin with following low thermal coefficient of expansion, high-tensile and high-modulus.The example of additive includes, but is not limited to: tackifier, coloring agent, pigment, antioxidant, heat stabilizer, ultra-violet stabilizer, fireproof agent, levelling agent, organic solvent, crosslinking agent and organic solvent.
Second embodiment such as concentrated-solidification of silicon resin composition can also comprise that molecular formula is R 3 qSiX 4-qCrosslinking agent, R wherein 3, the crosslinking agent among first embodiment that mentions in X and q such as the preceding text.Crosslinking agent can be the mixture of independent a kind of silane above-mentioned or two or more silane.
In use, the crosslinker concentration of second embodiment of concentrated-solidification of silicon resin composition enough is cured the silicones of the modified rubber of (crosslinked) composition (A).The actual amount of crosslinking agent depends on the degree of required curing, and it generally increases along with the increase of the ratio of the molal quantity of the hydrogen atom, hydroxyl or the hydrolysising group that are connected with silicon atom in the molal quantity of the hydrolysising group that links to each other with silicon atom in the crosslinking agent and the modified rubber silicones.Usually, add online concentration and enough 0.2 to 4 mole the hydrolysising group that links to each other with silicon atom is provided for hydroxyl or the hydrolysising group that links to each other with silicon atom in every mole of modified rubber silicones.The preferable amount of crosslinking agent can obtain by conventional experimental technique very soon.
The curable synthetic that comprises by thermosetting polymer can further include the carbon nanomaterial as mentioning in the preceding text.In practical application, the common concentration of carbon nanomaterial is 0.0001% to 99% (w/w) of thermosetting polymer gross weight, or 0.001% to 50% (w/w), or 0.01% to 25% (w/w), or 0.1% to 10% (w/w), or 1% to 5% (w/w).
Barrier film can adopt traditional coating technique to be coated with by the curable synthetic that includes thermosetting polymer, for example method of spin coating, embathe method, spraying process, brushing method, extrusion or silk screen print method.It is first polymeric layer of 0.01 μ m to 1000 μ m that the amount of synthetic (ii) enough forms thickness after the polymer cure in following method step.
The preparation first polymeric layer method before back to back step (ii) in, thermosetting polymer is cured in the barrier film that is applied.Thermosetting polymer can use several different methods to be cured, comprise say under the temperature that polymer is exposed under the environment temperature, raises, damp condition is down or under the radiation condition, select according to the difference of the curable synthetic that is used to be coated with barrier film.
When the curable synthetic that is used for being coated with barrier film for concentrate-during the solidification of silicon synthetic; And this synthetic comprises at least a silicones; At least two hydrolysising groups that link to each other with silicon atom are on average arranged in its each molecule, and the silicones of the barrier film that is applied can be through being heating and curing under the temperature of enough solidification of silicon resins.For example, silicones can heat 1 hour to 50 hours to coating usually in 50 ℃ to 250 ℃ scopes, be cured.When concentrate-when the solidification of silicon synthetic comprised catalyst concentration, silicones can for example be cured between room temperature (about 23 ± 2 ℃) is to 200 ℃ usually at low temperatures.
When the curable synthetic that is used for being coated with barrier film be comprise the silicones that has at least two hydrogen atoms that are connected with silicon at least a average each molecule (for example concentrate-among first embodiment of solidification of silicon synthetic silicones) concentrated-during the curing synthetic; Silicones can be through being exposed to coating under humidity or the oxygen condition; Between 100 ℃ to 450 ℃; Reach 0.1 hour to 20 hours, be cured.When concentrating-solidifying synthetic and comprise catalyst concentration, silicones usually can be under lower temperature, as between room temperature (about 23 ± 2 ℃) is to 400 ℃, being cured.
In addition; When the curable synthetic that is used for being coated with barrier film be comprise at least a average each molecule have at least two hydrogen atoms that are connected with silicon silicones concentrated-during the curing synthetic; Silicones can be through being exposed to coating in the wet environment, and room temperature (about 23 ± 2 ℃) is between 250 ℃, or between 100 ℃ to 200 ℃; Reach 1 to 100 hour, be cured.For example, it is 30% that silicones can be exposed to relative humidity with coating usually, and temperature is a room temperature (about 23 ± 2 ℃) between 150 ℃, reaches 0.5 to 72 hour, is cured.Heat, be exposed in the high humidity environment and/or increase catalyst concn and can quicken to solidify.
Silicones can be cured under atmospheric pressure or sub-atmospheric pressures.For example, when coating was not enclosed between two barrier films, silicones was cured in air under atmospheric pressure usually.Perhaps, when coating is closed between first and second barrier films, be described below, silicones under low pressure is cured usually.For example, silicones can be under 1000Pa to 20000Pa pressure, or under 1000Pa to the 5000Pa pressure, heat.Silicones can under low pressure use traditional vacuum bag means to be cured.In conventional method; The barrier film that dividing potential drop agent (like polyester) is used to be applied, absorbent (like nylon, polyester) is used in the dividing potential drop agent, and the vacuum coating (like nylon) that disposes vacuum nozzle is used on the absorbent; Said lamination is closed with adhesive tape; The lamination that is closed is applied vacuum pressure (like 1000Pa), and if necessary, the lamination that is vacuumized can heat by mentioned above.
The method for preparing first polymeric layer, wherein this layer comprises thermosetting polymer, can further include; Step (i) afterwards step (ii) before; On the barrier film of the coating that the first step is obtained second barrier film is set, forms lamination, and this lamination is suppressed.This lamination can through compacting remove more than synthetic and/or be wrapped in air wherein, and the thickness that reduces coating.Can use legacy equipment, suppress like stainless steel rider, hydraulic pressure, rubber rollers or lamination combination roller.Lamination is suppressed in the temperature range between the pressure of 1000Pa to 10MPa, room temperature (about 23 ± 2 ℃) are to 50 ℃ usually.
The method for preparing first polymeric layer, wherein this layer comprises thermosetting polymer, can further include step (i) and repetition (ii), to increase the thickness of polymeric layer, prerequisite is that each application step all adopts identical curing synthetic.
When first polymeric layer comprised thermoplastic polymer and fabric reinforcement, polymeric layer can be through (a) impregnation of fibers reinforce in the synthetic that includes the liquid thermoplastic polymer, and (b) thermoplastic polymer with the fabric reinforcement dipping is converted into solid-state.
In the step (a) that before the preparation first polymeric layer preparation method, is right after, fabric reinforcement is flooded in the synthetic that includes the liquid thermoplastic polymer.
Can adopt several different methods in the synthetic that includes the liquid thermoplastic polymer, fabric reinforcement to be flooded.For example, according to first method, fabric reinforcement can be applied on the barrier film through the synthetic that (i) will include the liquid thermoplastic polymer, forms film; (ii) on film, implant fabric reinforcement; (iii) synthetic is applied to and forms the impregnation of fibers reinforce on the fabric reinforcement of implantation.
In the step (i) that is right after before the impregnation of fibers reinforce, the synthetic that comprises the liquid thermoplastic polymer is applied to and forms film on the barrier film.Barrier film and synthetic are all as indicated above.Can adopt traditional coating process to apply synthetic, like method of spin coating, embathe method, spraying process, brushing method, extrusion or silk screen print method.The amount of the synthetic that is applied is enough implanted following step fabric reinforcement (ii).
Step (ii) in, fiber has been implanted in the film.Fabric reinforcement such as said.Fabric reinforcement can simply place reinforce on the film, and the synthetic of film is soaked into it.
Step (iii) in, the synthetic that includes the liquid thermoplastic polymer is applied on the fabric reinforcement of implantation, forms the fabric reinforcement of dipping.Can adopt the conventional method described in the step (i) that synthetic is applied on the fabric reinforcement of implantation.
The first method of impregnation of fibers reinforce can further include step (iv), second barrier film is applied on the fabric reinforcement of dipping and forms lamination; And step (v) compressed stack.In addition, first method can also step (ii) and step further comprise between (iii): the fabric reinforcement of implanting is carried out bleeding and/or step (iii) and step (iv) between, the fabric reinforcement of dipping is carried out bleeding.
Can suppress lamination and get rid of unnecessary synthetic and/or be wrapped in air wherein, to reduce the thickness of impregnation of fibers reinforce.Can use legacy equipment such as stainless steel rider, hydraulic pressure, rubber rollers or lamination combination roller that lamination is suppressed.Lamination is suppressed in the temperature range between the pressure of 1000Pa to 10MPa, room temperature (about 23 ± 2 ℃) are to 200 ℃ usually.
The fabric reinforcement of implanting or the fabric reinforcement of dipping can apply vacuum and carry out exhaust under the temperature of the fluid state that enough keeps thermoplastic polymer.
Perhaps, according to second method, fabric reinforcement can be carried out through following steps: (i) fabric reinforcement is placed on the barrier film at the dipping in the synthetic that comprises the liquid thermoplastic polymer; (ii) fabric reinforcement is implanted in the synthetic that includes the liquid thermoplastic polymer; (iii) synthetic is applied on the fabric reinforcement of implantation, forms the impregnation of fibers reinforce.Second method can further include step (iv), second barrier film is applied on the fabric reinforcement of dipping and forms lamination; And (v) compressed stack.In the second approach, step is (iii) to (v) as the first method of impregnation of fibers reinforce in comprising liquid state and have the synthetic of thermoplastic polymer.In addition, first method can also step (ii) and step further comprise between (iii): the fabric reinforcement of implanting is carried out bleeding and/or step (iii) and step (iv) between, the fabric reinforcement of dipping is carried out bleeding.
The step that is right after before the impregnation of fibers reinforce (ii) in, fabric reinforcement is immersed in the synthetic that comprises the liquid thermoplastic polymer.Fabric reinforcement can make synthetic soak into reinforce through the simple mode that on reinforce, covers synthetic, thereby fabric reinforcement is implanted in the synthetic.
In addition, when fabric reinforcement was fabric or non-woven fleece, reinforce can pass the synthetic that comprises the liquid thermoplastic polymer, to reach the effect of dipping.The speed that fabric or non-woven fleece pass synthetic is 1 cm per minute to 1000 cm per minute.
In the step (b) that before the method for preparation first polymeric layer, is right after, the thermoplastic polymer in the impregnation of fibers reinforce becomes solid-state.When the synthetic that is used for being coated with barrier film comprised the thermoplastic polymer of molten state, thermoplastic polymer can below room temperature, be transformed into solid-state through polymer being cooled to below the solid-liquid transformation temperature (Tg or Tm).When the synthetic that is used for being coated with barrier film included thermoplastic polymer and organic solvent, thermoplastic polymer can become solid-state through removing at least a portion solvent.Organic solvent can be at ambient temperature through the means of the solid-liquid transformation temperature of the method for evaporating solvent or heating coating to proper temperature such as polymer, be able to remove.
The method for preparing first polymeric layer; Wherein this layer comprises the synthetic and the fabric reinforcement of the thermoplastic resin of fluid state; Can further include step (a) and the thickness that repeats to increase polymeric layer (b), prerequisite is in each dipping, to adopt identical synthetic.
When first polymeric layer comprised thermosetting polymer and fabric reinforcement, polymer can be through (a ') impregnation of fibers reinforce in including the curable synthetic of thermosetting polymer; (b ') thermosetting polymer in the impregnation of fibers reinforce is cured.
The step that before the method for preparation first polymeric layer, is right after (a ') in, fabric reinforcement is immersed in the curable synthetic that includes thermosetting polymer.Fabric reinforcement and synthetic are as indicated above.Fabric reinforcement can utilize mentioned above in including the synthetic of thermoplastic polymer the method for impregnation of fibers reinforce in curable synthetic, flood.
The step that before the method for preparation first polymeric layer, is right after (b ') in, the thermosetting polymer in the impregnation of fibers reinforce is cured.Can adopt several different methods, comprise the impregnation of fibers reinforce is exposed in the temperature of environment temperature or rising, under humidity or the radiation condition, selects according to being used for the kind of curable synthetic of impregnation of fibers reinforce, thermosetting polymer is cured.
When being used for the curable synthetic of impregnation of fibers reinforce is to include concentrating-the solidification of silicon resin composition of at least a silicones; And on average have two in this silicones per molecule at least during with hydroxyl that silicon atom is connected; Silicones can be through under the temperature of enough solidification of silicon resins; Heating impregnation of fibers reinforce, the solidification of silicon resin.For example, silicones usually can 50 ℃ under 250 ℃, heating coating was cured in 1 hour to 50 hours.When concentrate-when the solidification of silicon synthetic comprised catalyst concentration, silicones usually can be at a lower temperature, as being cured in the temperature range of room temperature (about 23 ± 2 ℃) between 200 ℃.
Comprise at least a silicones when being used for the concentrating of curable synthetic-solidification of silicon synthetic of impregnation of fibers reinforce; When having two hydrogen atoms that link to each other with silicon (silicones among first embodiment of for example concentrated-curing synthetic) in average each molecule of this silicones at least; Silicones can be through being exposed to the impregnation of fibers reinforce under humidity or the oxygen condition; Temperature is 100 ℃ to 450 ℃, reaches 0.1 hour to 20 hours, is cured.When concentrate-when the solidification of silicon synthetic comprised catalyst concentration, silicones usually can be at a lower temperature, as being cured in the temperature range of room temperature (about 23 ± 2 ℃) between 400 ℃.
In addition; Comprise at least a silicones when being used for the concentrating of curable synthetic-solidification of silicon synthetic of impregnation of fibers reinforce, have two in average each molecule of this silicones at least during with hydrolysising group that silicon links to each other, silicones can be through being exposed to the impregnation of fibers reinforce under the wet condition; Room temperature (about 23 ± 2 ℃) is between 250 ℃; Or in the temperature range between 100 ℃ to 200 ℃, reach 1 to 100 hour, be cured.For example, silicones can be 30% through the impregnation of fibers reinforce being exposed to relative humidity usually, and temperature reaches 0.5 to 72 hour between room temperature (about 23 ± 2 ℃) is to 150 ℃, be cured.Through heating, contact high humidity environment and/or interpolation catalyst concentration acceleration curing in synthetic.
Silicones in the impregnation of fibers reinforce can be under atmospheric pressure or sub-atmospheric pressures, and according to the difference of above-mentioned method therefor, the means of impregnation of fibers reinforce are cured in concentrated-solidification of silicon synthetic.For example, when coating was not enclosed between two barrier films, silicones was cured in air under atmospheric pressure usually.Perhaps, when coating was closed between first and second barrier films, silicones under low pressure was cured usually.For example, silicones can be under 1000Pa to 20000Pa pressure, or under 1000Pa to the 5000Pa pressure, heat.Silicones can under low pressure use traditional vacuum bag means to be cured.In conventional method; The barrier film that dividing potential drop agent (like polyester) is used to be applied, absorbent (like nylon, polyester) is used in the dividing potential drop agent, and the vacuum coating (like nylon) that disposes vacuum nozzle is used on the absorbent; Said lamination is closed with adhesive tape; The lamination that is closed is applied vacuum pressure (like 1000Pa), and if necessary, the lamination that is vacuumized can heat by mentioned above.
The method for preparing first polymeric layer; Wherein this layer comprises thermosetting polymer and fabric reinforcement; May further include the thickness that repeats to increase polymeric layer to step (a ') and (b '), prerequisite is in each dipping, to adopt identical curable synthetic.
Strengthen in preparation method's second step of silicone resin film first, above-mentioned the second polymer layer is formed on first polymeric layer.The second polymer layer can be like the preparation of the method for above-mentioned preparation first polymeric layer, and wherein the second polymer layer is formed on first polymeric layer, but not exception on the barrier film time.
The method that preparation first strengthens silicone resin film further comprises separates first polymeric layer with barrier film.First polymeric layer can separate with barrier film before or after the second polymer layer forms.In addition, first polymeric layer can separate it through the method for mechanical stripping from barrier film.
Among the present invention second strengthens silicone resin film and comprises:
First polymeric layer;
The second polymer layer on first polymeric layer; And
The polymeric layer that at least one is other, this layer are at least on first polymeric layer or on its middle level of the second polymer layer; Wherein at least one polymeric layer comprises the solidfied material of at least a silicones, have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in average each molecule of this silicones, and at least one polymeric layer comprises carbon nanomaterial.
Second to strengthen the common thickness of silicone resin film be 0.01 μ m to 1000 μ m, or 5 μ m to 500 μ m, again or 10 μ m to 100 μ m.
First polymeric layer of the second enhancing silicone resin film can comprise thermoplasticity or thermosetting polymer.Thermoplasticity and thermosetting polymer strengthen described in the silicone resin film related content as first.
Except thermoplasticity or thermosetting polymer, first polymeric layer of the second enhancing silicone resin film can comprise carbon nanomaterial, fabric reinforcement or their mixture, and they are as indicated above separately.
The second polymer layer and the said other polymeric layer of the second enhancing silicone resin film are of the first polymeric layer related content.On a kind of physics and chemical property, there are differences at least of the adjacent layer of the second enhancing silicone resin film comprises the concentration of thickness, the degree of polymerization, the degree of cross linking, carbon nanomaterial concentration or additive.
Second strengthens silicone resin film generally includes 1 layer to 100 layers additional polymer, or 1 layer to 10 layers additional polymer, or 2 layers to 5 layers additional polymer.
At least one polymeric layer of the second enhancing silicone resin film comprises the cured product of at least one silicones, has at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in average each molecule of this silicones.Silicones, the method for preparing the method for this resin and prepare the silicones cured article are identical with the preparation method about the present invention's first enhancing silicone resin film mentioned above.
At least one one polymer layer of the second enhancing silicone resin film comprises carbon nanomaterial.The concentration of carbon nanomaterial, carbon nanomaterial and the method for preparing carbon nanomaterial are identical with the first enhancing silicone resin film mentioned above.
First polymeric layer, the second polymer layer and other polymeric layer can prepare according to the preparation method of the second enhancing silicone resin film among the present invention.
The preparation method of the second enhancing silicone resin film comprises:
On barrier film, form first polymeric layer;
On first polymeric layer, form the second polymer layer; And
On first polymeric layer or on one of them layer of the second polymer layer, form at least one other polymeric layer; Wherein at least one polymeric layer comprises the solidfied material of at least a silicones, have at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in each molecule of this silicones, and at least one polymeric layer comprises carbon nanomaterial.
First polymeric layer, the second polymer layer and other polymeric layer can prepare according to the preparation method of the first enhancing silicone resin film mentioned above.
Enhancing silicone resin film of the present invention generally includes 1% to 99% (w/w), or 10% to 95% (w/w), or 30% to 95% (w/w), or the solidification of silicon resin of 50% to 95% (w/w).In addition, strengthening the common thickness of silicone resin film is 1 μ m to 3000 μ m, or 15 μ m to 500 μ m, or 15 μ m to 300 μ m, or 20 μ m to 150 μ m, or 30 μ m to 125 μ m.
Strengthen silicone resin film and have pliability usually, can be less than or equal to 3.2 millimeters cylindrical shape iron and steel axle around diameter and carry out bending and do not fracture, pliability is according to ASTM standard D522-93a here, and method B assert.
The enhancing silicone resin film has low thermal linear expansion coefficient (CTE), high-tensile, high-modulus and high heat resistanceheat resistant and causes tear resistance.For example, usually the CTE of film is 0 to 80 μ m/m ℃, or 0 to 20 μ m/m ℃, or 2 to 10 μ m/m ℃, temperature from room temperature (about 23 ± 2 ℃) to 200 ℃.In addition, in the time of 25 ℃, the tensile strength of film is 5MPa to 200MPa usually, or 20MPa to 200MPa, or 50MPa to 200MPa.In addition, in the time of 25 ℃, strengthening the common yang type modulus of silicone resin film is 0.5GPa to 10GPa, or 1GPa to 6GPa, or 3GPa to 5GPa.
The light transmission that strengthens silicone resin film depends on some factors, like composition, the thickness of film and the type and the concentration of reinforce of the silicones that solidifies.In the viewing area of electromagnetism chromatogram, strengthen the common light transmittance of silicone resin film (% visibility) and be at least 5%, or at least 10%, or at least 15%, or at least 20%.
Among the present invention, strengthen silicone resin film and can be applicable to require film to have the situation of high thermal stability, pliability, mechanical strength and light transmission.For example, silicone resin film can be as integrated component, solar cell, flexible PCB, touch-screen, fire prevention wallpaper and the high strength window of flexible display.This film also is applicable to the substrate of transparent or opaque electrode.
Example
Following each example can better explain describe in claims about enhancing silicone resin film of the present invention and preparation method thereof, but be not regarded as limiting of the invention.Except that other had explanation, all marks and percentage all were by weight in the example.Following material is used for example:
Pyrograf
Figure G2008800060503D00201
-III; HHT-19 level carbon nano-fiber is by Pyrograf Products; Inc. (Cedarville Ohio) sells, and it is the carbon nano-fiber through heat treatment (going up to 3000 ℃); Diameter is 100nm to 200nm; Length is 30,000nm to 100,000nm.
The brilliant coating resin of SDC MP101, by SDC Technologies, (Anaheim CA) sells Inc., and it is the solution that contains 31% (w/w) silicones, mainly by MeSiO 3/2Unit and SiO 4/2The unit is dissolved in methane, 2 propyl alcohol, water and acetic acid (about 1 to the 2%) mixture.
Glass fabric is the 106 type plain weaves electricity glass fabric of 37.5 μ m for through heat treated glass fabric by thickness, makes in 6 hours 575 ℃ of heating.Undressed glass fabric is from JPS glass (Slater, SC) company.
Example 1
This example is depicted as the preparation process of the carbon nano-fiber of chemical oxidation.The nitric acid that Pyrograf
Figure G2008800060503D00202
-III carbon nano-fiber (2.0 gram) 12.5mL concentrates; And the sulfuric acid that 37.5mL concentrates is blended in the three-necked bottle of 500mL, and is furnished with condenser, thermometer, is coated with the magnet stirring rod and the temperature controller of Teflon.Mixture is heated to 80 ℃, and kept this temperature 3 hours.Afterwards three-necked bottle is placed on the dry ice layer of a GPB mixture is cooled off.Mixture is poured in the Bi Xina funnel that contains nylon membrane (0.8 μ m) and carbon nano-fiber, collected with vacuum filter.The nanofiber that is retained on the film cleans several times through deionized water repeatedly, equals the pH value of rinse water until the pH value that leaches thing.After having cleaned for the last time, carbon nano-fiber is retained in to be treated in the funnel 15 minutes again, and constantly applied vacuum.Nanofiber is supported by filter membrane afterwards, places 100 ℃ baking box 1 hour.Carbon nano-fiber takes off from filter membrane, is kept in the dry sealed glass jar.
Example 2
Carbon nano-fiber (0.031 gram) and the brilliant coating resin of 50.0 gram SDC MP101 through oxidation in the example 1 are put into vial together.Vial was positioned over ultrasonic environment following 30 minutes.Mixture carries out centrifugal filtration in 30 minutes under the rotating speed of 2000 rev/mins (rpm) afterwards.To clarify compound and strengthen silicone resin film by following content preparation.
Example 3
With the speed of glass fabric (38.1cmx8.9cm), pass the brilliant coating resin of MP101, thereby be able to dipping with 5cm/s.Vertically hang in fume hood after the fabric behind the dipping, at room temperature dry, afterwards in the baking box of circulation of air; Undertaken by following step cycle: the speed with 1 ℃/min rises to 75 ℃ by room temperature; 75 ℃ kept 1 hour, rose to 100 ℃ with the speed of 1 ℃/min by 75 ℃, kept 1 hour at 100 ℃; Speed with 1 ℃/min rises to 125 ℃ by 100 ℃, keeps 1 hour at 125 ℃.After baking box was closed, silicone resin film was able to be cooled to room temperature.
The silicon synthetic of carbon nano-fiber filling in the example 2 is diluted to 20.75% (w/w) with 2 propyl alcohol obtains the silicon synthetic, film is flooded therein.After flooding first, according to step mentioned above fabric drying, curing to dipping.
The silicone resin film of three layers of enhancing under the nitrogen environment, is heat-treated by following condition in baking box again: the speed with 5 ℃/min rises to 575 ℃ by room temperature, keeps 1 hour at 575 ℃.Baking box is turned off, and strengthens silicone resin film and is able to be cooled to room temperature.Figure 1A (front view) and Figure 1B (viewgraph of cross-section) are the microphoto of heat treatment cephacoria.Fig. 1 C is the microphoto that strengthens silicone resin film after the heat treatment.Heat treated film does not have tear trace.
Comparative Examples 1
According to the silicone resin film that the preparation of example 3 method does not strengthen, just MP101 crystalline substance coating resin is diluted to 20.75% (w/w) and the silicones synthetic that obtains carries out double-steeping with 2 propyl alcohol.
After the curing, three layers silicone resin film is heat-treated by following condition in the baking box of circulating air: the speed with 5 ℃/min rises to 400 ℃ by room temperature, keeps 1 hour at 400 ℃.Turn off baking box, film is able to be cooled to room temperature.The microphoto of the silicone resin film before and after the heat treatment is presented at respectively among Fig. 2 A and the 2B.Film after the heat treatment has a large amount of tear traces.
Example 4
Strengthen silicone resin film according to the preparation of example 3 method, just MP101 crystalline substance coating resin is diluted to 10.35% (w/w) and the silicones synthetic that obtains carries out double-steeping with 2 propyl alcohol.
After the curing, three layers silicone resin film is heat-treated by following condition in the baking box of nitrogen environment: the speed with 5 ℃/min rises to 575 ℃ by room temperature, keeps 1 hour at 575 ℃.Turn off baking box, film is able to be cooled to room temperature.The microphoto of the silicone resin film before the heat treatment is presented among Fig. 3.Film after the heat treatment does not have tear trace.
Example 5
Prepare the enhancing silicone resin film according to example 3 method, 2 propyl alcohol are diluted to 10.35% (w/w) with the brilliant coating resin of MP101 and the silicones synthetic that obtains, will strengthen silicone resin film and flood therein.Said film is carried out drying, curing according to example 3.
5 layers enhancing silicone resin film is heat-treated by following condition in the baking box of nitrogen environment: the speed with 5 ℃/min rises to 575 ℃ by room temperature, keeps 1 hour at 575 ℃.Turn off baking box, film is able to be cooled to room temperature.The microphoto of the silicone resin film before the heat treatment is presented among Fig. 4.Film after the heat treatment does not have tear trace.
Comparative Examples 2
Method based on example 3 prepares the silicone resin film that does not strengthen.Just MP101 crystalline substance coating resin is diluted to 10.35% (w/w) and the silicones synthetic that obtains carries out double-steeping with 2 propyl alcohol.3 layers of silicone resin film after the curing are once more with the brilliant coating resin dipping of the MP101 of dilution.Said film is carried out drying, curing according to example 3.
5 layers enhancing silicone resin film is heat-treated by following condition in the baking box of nitrogen environment: the speed with 5 ℃/min rises to 575 ℃ by room temperature, keeps 1 hour at 575 ℃.Turn off baking box, film is able to be cooled to room temperature.Before heat treatment, with the observation by light microscope that amplifies 100 times, about 14% surface area has tear trace on the film, and after the heat treatment, about 55% surface area has the microcosmic tear trace on the film.

Claims (13)

1. one kind strengthens silicone resin film, it is characterized in that mainly by constituting as follows:
First polymeric layer and
The second polymer layer on first polymeric layer; Wherein at least one polymeric layer comprises the cured product of at least a silicones; And contain at least two hydrogen atoms that link to each other with silicon atom, hydroxyl or hydrolysising groups in average each molecule of this silicones; And at least one polymeric layer comprises carbon nanomaterial; If two polymeric layers are when all comprising the cured product of silicones, two polymeric layers all comprise and are selected from (i) carbon nanomaterial, (ii) fabric reinforcement and (iii) comprise (i) and the reinforce of mixture (ii).
2. enhancing silicone resin film according to claim 1 is characterized in that wherein the thickness of first polymeric layer and the second polymer layer is 0.01 to 1000 μ m.
3. enhancing silicone resin film according to claim 1, it is characterized in that wherein first polymeric layer and the second polymer layer one of them comprises the reinforce that is selected from carbon nanomaterial, fabric reinforcement and both mixtures thereof at least.
4. enhancing silicone resin film according to claim 1 is characterized in that wherein the silicones molecular formula is (R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) z(I), R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 2Be R 1,-H ,-OH or hydrolysising group, w is 0 to 0.95, x is 0 to 0.95; Y is 0 to 1, and z is 0 to 0.95, w+x+y+z=1; Y+z is 0.05 to 1, and w+x is 0 to 0.95, and contains at least two hydrogen atoms that are connected with silicon, oh group or hydrolysising groups in average each molecule of silicones.
5. enhancing silicone resin film according to claim 1 is characterized in that wherein silicones is the silicones of modified rubber, and the silicones of this modification is through being selected from (i): molecular formula is (R 1R 4 2SiO 1/2) w(R 4 2SiO 2/2) x(R 4SiO 3/2) y(SiO 4/2) z(II) silicones and (ii): the organo-silicon compound of hydrolysis precursor (i), with molecular formula be R 5 3SiO (R 1R 5SiO) mSiR 5 3(III) silicon rubber reacts under the existence condition of the organic solvent of water, catalyst concentration and formation soluble reaction product and to make, wherein R 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 4Be R 1,-OH, R 5Be R 1Or hydrolysising group, m is 2 to 1000, w is 0 to 0.95; X is 0 to 0.95, and y is 0 to 1, and z is 0 to 0.95; W+x+y+z=1; Y+z is 0.05 to 1, and w+x is 0 to 0.95, and silicones (II) on average all contains at least two hydroxyls that link to each other with silicon atom or hydrolysising group in each molecule; Silicon rubber (III) on average contains at least two hydrolysising groups that link to each other with silicon atom in each molecule, and the hydroxyl that is connected with silicon in the hydrolysising group that is connected with silicon in the silicon rubber (III) and the silicones (II) or the mol ratio of hydrolysising group are 0.01 to 1.5.
6. enhancing silicone resin film according to claim 1 is characterized in that wherein at least one polymeric layer comprises the carbon nanomaterial that is selected from carbon nano-particle, fibrous carbon nano material and layered carbon nano material.
7. one kind strengthens silicone resin film, it is characterized in that comprising:
First polymeric layer;
The second polymer layer on first polymeric layer; And
At least one additional polymer on one of them at least at first and second polymeric layers; Wherein at least one polymeric layer comprises the cured product of at least a silicones, and contains at least two hydrogen atoms that are connected with silicon, hydroxyl or hydrolysising groups in average each molecule of this silicones, and at least one polymeric layer comprises carbon nanomaterial.
8. enhancing silicone resin film according to claim 7 is characterized in that wherein the thickness of first polymeric layer, the second polymer layer and additional polymer is 0.01 μ m to 1000 μ m.
9. enhancing silicone resin film according to claim 7 is characterized in that wherein this film comprises three polymeric layers.
10. enhancing silicone resin film according to claim 7 is characterized in that wherein at least one polymeric layer comprises the reinforce that is selected from carbon nanomaterial, fabric reinforcement and both mixtures.
11. enhancing silicone resin film according to claim 7 is characterized in that wherein the molecular formula of silicones is (R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) z(I), R wherein 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 2Be R 1,-H ,-OH or hydrolysising group, w is 0 to 0.95, x is 0 to 0.95; Y is 0 to 1, and z is 0 to 0.95, w+x+y+z=1; Y+z is 0.05 to 1, and w+x is 0 to 0.95, and contains at least two hydrogen atoms that link to each other with silicon atom, oh group or hydrolysising groups in average each molecule of silicones.
12. enhancing silicone resin film according to claim 7 is characterized in that wherein silicones is the silicones of modified rubber, the silicones of this modification is through being selected from (i): molecular formula is (R 1R 4 2SiO 1/2) w(R 4 2SiO 2/2) x(R 4SiO 3/2) y(SiO 4/2) z(II) silicones and (ii): the organo-silicon compound of hydrolysis precursor (i), with molecular formula be R 5 3SiO (R 1R 5SiO) mSiR 5 3(III) silicon rubber reacts under the existence condition of the organic solvent of water, catalyst concentration and formation soluble reaction product and to make, wherein R 1Be C 1To C 10Alkyl or C 1To C 10The halo alkyl, R 4Be R 1,-OH or hydrolysising group, R 5Be R 1Or hydrolysising group, m is 2 to 1000, w is 0 to 0.95; X is 0 to 0.95, and y is 0 to 1, and z is 0 to 0.95; W+x+y+z=1; Y+z is 0.05 to 1, and w+x is 0 to 0.95, and silicones (II) on average all contains at least two hydroxyls that link to each other with silicon atom or hydrolysising group in each molecule; Silicon rubber (III) on average contains at least two hydrolysising groups that link to each other with silicon atom in each molecule, and the hydroxyl that is connected with silicon in the hydrolysising group that is connected with silicon in the silicon rubber (III) and the silicones (II) or the mol ratio of hydrolysising group are 0.01 to 1.5.
13. enhancing silicone resin film according to claim 7 is characterized in that wherein at least one polymeric layer comprises the carbon nanomaterial that is selected from carbon nano-particle, fibrous carbon nano material and layered carbon nano material.
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